CN101717507A - Static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber - Google Patents
Static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber Download PDFInfo
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- CN101717507A CN101717507A CN200910310026A CN200910310026A CN101717507A CN 101717507 A CN101717507 A CN 101717507A CN 200910310026 A CN200910310026 A CN 200910310026A CN 200910310026 A CN200910310026 A CN 200910310026A CN 101717507 A CN101717507 A CN 101717507A
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Abstract
The invention provides a static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber, belonging to the technical field of conducting polymer material. The invention solves the problems that the traditional polymerization method of preparing the conducting polyaniline nano-fiber needs an additional template, has complicated after-treatment processes, pollutes the environment by the used solvent, produce less polymers, is not suitable for mass production, and the like. In the invention, the aniline and the sulfoacid aniline are used as monomers, and the static chemical oxidation polymerization implementation method is used for preparing the polyaniline nano-fiber. The method can be used for preparing the polyaniline nano-fiber which is 30-95nm in diameter and 1.6 micrometers in length. The method of the invention has the characteristics of simple operation, high yield and low cost, belongs to the aqueous system and does not relate to organic solvents, is an environment-friendly method of synthesizing the polyaniline nano-fiber, and provides a new way for synthesizing the polyaniline nano-fiber.
Description
Technical field
The invention belongs to the preparing technical field of functional polymer nano material, more specifically relate to a kind of synthetic method of aniline-sulfoacid aniline copolymer nano-fiber.
Background technology
Electrically conductive polyaniline nano fiber has the specific conductivity height, environmental stability is good, specific surface area is big, electroactive big, excellent characteristics such as oxidation-reduction quality is good, and it is had wide practical use in fields such as transmitter, ultracapacitor, energy storage material, secondary cell, electron devices.The method that is used to prepare polyaniline nano fiber at present has method of electrostatic spinning (Kahol P.K.; PintoN.J.Synth.Met.2004,140,269.Aussawasathien D.; Dong J.H.; Dai L.Synth.Met.2005,154,37.He C.; Tan Y.W.; Li Y.F.J.Appl.Polym.Sci.2003,87,1537.), template synthesis method (Martin C.R.Science 1994,266,1961.) and do not have the template synthesis method, as interfacial polymerization (Virji S.; Huang J.X.; Kaner R.B.; Weiller B.H.Nano Lett.2004,4,491.Huang J.X.; Virji S.; Weiller B.H.; Kaner R.B.J.Am.Chem.Soc.2003,125,314.Zhang X.Y.; Chan-Yu-King R.; Jose A.; Manohar S.K.Synth.Met.2004,145,23.do Nascimento G.M.; Kobata P.Y.G.; Temperini M.L.A.J.Phys.Chem.B.; 2008,112,11551.), short mix reaction method (Huang J.X.; Kaner R.B.Angew.Chem.Int.Ed.2004,43,5817.Qiang J.F; Yu Z.H; Wu H.C.; Yun D.Q.Synth.Met.2008,158,544.), dilution polymerization (Chiou N.R.; Epstein A.J.Adv.Mater.2005,73,1679.), sonochemistry synthesis method (Jing X.L.; Wang Y.Y.; Wu D.; QiangJ.P.Ultrason.Sonochem.2007,14,75.), seeding polymerization method (Zhang X.Y.; Goux W.J.; Manohar S.K.J.Am.Chem.Soc.2004,126,4502.Xing S.X.; Zheng H.W.e-Polymers 2008, no.106.) electrochemical polymerization method (Guo Y.P.; Zhou Y.Eur.Polym.J.2007,43,2292.) etc.More than be used for preparing the method for polyaniline nano fiber, the template synthesis method is efficient ways, and it can well regulate and control diameter, length and the directivity of nanofiber.Yet the main drawback of this method is the preparation of template, use and the removal process comparatively numerous and diverse, not only increase technical process, and destroy the nanostructure of template interpolymer easily.As the interfacial polymerization of one of no template, be the simple and easy method that single stage method prepares the homogeneous polyaniline nano fiber, but dissolving aniline monomer need organic solvent and can cause environmental pollution.Short mix polymerization and dilution polymerization are also comparatively simple, but the productive rate of the polyaniline for preparing is lower, is not suitable for mass production and application.
Therefore, the novel method of setting up a kind of pollution-free, simple and effective preparation high yield electrically conductive polyaniline nano fiber still is an important problem in science.
Summary of the invention
The objective of the invention is in order to overcome and to solve needing that the synthetic method of existing preparation electrically conductive polyaniline nano fiber exists additional template, postprocessing working procedures complexity or resulting polymers productive rate are low, the solvent for use contaminate environment, be difficult to shortcoming and problem such as mass production, research provides a kind of synthetic method of pollution-free, simple to operate, electrically conductive polyaniline nano fiber that polymerization yield rate is high, and this method is a kind of in the method that does not have to prepare under the additional template condition electrically conductive polyaniline nano fiber.The present invention implements means by static chemical oxidative polymerization, at the multipolymer that makes aniline and sulfoacid aniline under the situation of no template direct nanometer when synthetic; Product is productive rate height, the good polyaniline nano fiber of electrical property.Operation is simple for this method, has unique application prospect aspect the preparation polyaniline nano fiber.
The static synthesis method of a kind of aniline-sulfoacid aniline copolymer nano-fiber of the present invention: under static conditions, be reaction medium solution, aniline and sulfoacid aniline derivative are dissolved in reaction medium solution with the acidic solution; Oxygenant is dissolved in a kind of reaction medium solution, two kinds of solution are mixed, make oxygenant cause aniline and sulfoacid aniline polymerization reaction take place, temperature of reaction is 0～30 ℃, reaction times is 1～72 hour, obtains containing the polymers soln of copolymer nano fiber, and polymers soln is filtered, drying is 7 days under 60 ℃, gets the aniline-sulfoacid aniline copolymer nano-fiber powdered sample.
Remarkable advantage of the present invention is: the present invention adopts the static polymerization of no template, in acid reaction medium, and acquisition size homogeneous, the aniline-sulfoacid aniline copolymer nano-fiber that the pattern controllability is good.Simple to operate, and can solve the low problem of polymer yield, the resulting polymers nanofiber can be applied to prepare transmitter, super capacitor material and adsorbent for heavy metal etc., can solve the processing difficult problem of polyaniline well, has expanded their Application Areas.The preparation method is simple, need not additional template, has simplified synthesis technique, and this method is water-based system, does not relate to organic solvent, is a kind of method of synthetic copolymer fiber green.
Description of drawings
Fig. 1 is the TEM photo of the prepared aniline-sulfoacid aniline copolymer nano-fiber of embodiment 1.
Fig. 2 is the TEM photo of the prepared aniline-sulfoacid aniline copolymer nano-fiber of embodiment 2.
Fig. 3 is the TEM photo of the prepared aniline-sulfoacid aniline copolymer nano-fiber of embodiment 3.
Fig. 4 is the TEM photo of the prepared aniline-sulfoacid aniline copolymer nano-fiber of embodiment 4.
Fig. 5 is the TEM photo of the prepared aniline-sulfoacid aniline copolymer nano-fiber of embodiment 5.
Embodiment
Preparation method's concrete steps are:
(1) preparation monomer solution: monomer aniline and sulfoacid aniline derivatives monomer are joined in the reaction medium solution, stir and to make it abundant dissolving, form monomer solution, be put into then that constant temperature is to temperature of reaction in the reaction water-bath, described temperature of reaction is 0 to 30 ℃;
(2) preparation oxidizing agent solution: oxygenant is joined (same concentrations and same reaction medium) in the identical reaction medium solution of step (1), stirring makes it abundant dissolving, form oxidizing agent solution, be put into then that constant temperature is to temperature of reaction in the reaction water-bath, temperature of reaction is 0 to 30 ℃;
(3) mixing solutions, polyreaction: the oxidizing agent solution of described step (2) is dropwise joined initiated polymerization in the monomer solution of described step (1);
(4) continue reaction: after oxygenant dropwises, continue reaction 1～72 hour under static state, temperature of reaction is 0～30 ℃, and it is reacted completely, and obtains containing the polymers soln of copolymer nano fiber;
(5) preparation copolymer nano fiber: polymers soln is filtered, 60 ℃ dry 7 days down, the aniline-sulfoacid aniline copolymer nano-fiber powdered sample.
Working sample for the copolymer nano fiber, the polymers soln centrifuge washing that can get 2mL step (4) repeatedly, the gained clean product is distributed in the deionized water again, get aniline-sulfoacid aniline copolymer nanometer water sample sample, perhaps aniline-sulfoacid aniline copolymer the samples of nanopowders that also can directly adopt step (5) to prepare is distributed to and obtains sample in the deionized water.
In the above step:
The mol ratio of aniline and sulfoacid aniline derivative 90: 10～50: 50;
Described oxygenant can adopt a kind of in ammonium persulphate, Potassium Persulphate or the Sodium Persulfate; The mol ratio of described oxygenant and monomer total amount (aniline+sulfoacid aniline derivative) is 1: 4～2: 1, and optimum mole ratio is 1: 4～1: 1.
In the step (1): when aniline and sulfoacid aniline derivative were dissolved in the reaction medium solution, the total mol concentration of monomer (aniline+sulfoacid aniline derivative) was 0.025～0.5mol/L.The volumetric molar concentration of monomer the best is 0.05～0.1mol/L;
In the step (2), when oxygenant was dissolved in the identical reaction medium solution that step (1) uses, the volumetric molar concentration of oxygenant was 0.025～0.5mol/L, and the optimum molar concentration of oxygenant is 0.05～0.2mol/L.
The reaction medium solution that uses: acidic solution is a kind of in 0.2～3.0mol/L aqueous hydrochloric acid or the aqueous sulfuric acid as concentration, and optimum concn is 0.05～0.1mol/L.
Among the present invention, the comonomer of aniline-sulfoacid aniline copolymer nano-fiber is the sulfoacid aniline derivatives monomer shown in aniline and the chemical formula (1);
In the formula, R is respectively-H ,-C
6H
4SO
3H; R
1Be respectively-H ,-SO
3H ,-OCH
3R
2Be respectively-H ,-SO
3H.
Productive rate by the aniline-sulfoacid aniline copolymer nano-fiber of present method preparation is higher, can reach 83%, and the product specific conductivity can reach 0.73S/cm, and diameter is 30～95nm, and length can reach 1.6 microns.
Below be several specific embodiments of invention, further specify the present invention, but the present invention be not limited only to this.
Embodiment 1
Take by weighing the adjacent methoxy of 1mmol-5-sulfoacid aniline, place the dried and clean beaker, add the 1.0mol/L HCl aqueous solution, stir and make it abundant dissolving, measure 9mmol aniline then and add in the above-mentioned solution, in 0 ℃ of ice-water bath, stir 0.5h, get monomer mixed solution.Other takes by weighing the 10mmol ammonium persulphate and is dissolved in the 1.0mol/L HCl aqueous solution, stirs 0.5h to dissolving fully in 0 ℃ of ice-water bath, obtains colourless transparent solution.Speed with 1 of per second under static conditions drips ammonium persulfate aqueous solution in above-mentioned monomer mixed solution.After dropwising, continue to react to 24h.Reaction finishes, and gets 2mL reaction solution centrifuge washing, and sample is in order to do the test of polymkeric substance pattern, and the diameter of gained copolymer nano fiber is about 75～95nm, and length is 200～950nm.As shown in Figure 1.Residual reaction liquid is filtered, and filter cake drying under 60 ℃ got the deep green copolymer powder to constant weight in 7 days, and polymerization yield rate can reach 81%, and its specific conductivity is 0.57S/cm.
Embodiment 2
Take by weighing 1mmol ortho-sulfonic acid aniline, place the dried and clean beaker, add the 1.0mol/L HCl aqueous solution, stir and make it abundant dissolving, measure 9mmol aniline then and add in the above-mentioned solution, in 30 ℃ of ice-water baths, stir 0.5h, get monomer mixed solution.Other takes by weighing the 5mmol ammonium persulphate and is dissolved in the 1.0mol/L HCl aqueous solution, stirs 0.5h to dissolving fully in 0 ℃ of ice-water bath, obtains colourless transparent solution.Speed with 1 of per second under static conditions drips ammonium persulfate aqueous solution in above-mentioned monomer mixed solution.After dropwising, continue to react to 72h.Reaction finishes, and gets 2mL reaction solution centrifuge washing, and sample is in order to do the test of polymkeric substance pattern, and the diameter of gained copolymer nano fiber is about 30～55nm, and length is 200nm～1.6 micron.As shown in Figure 2.Residual reaction liquid is filtered, and filter cake drying under 60 ℃ got the deep green copolymer powder to constant weight in 7 days, and polymerization yield rate can reach 83%, and its specific conductivity is 0.73S/cm.
Embodiment 3
Take by weighing 1mmol 2,5-disulfonic acid aniline places the dried and clean beaker, adds the 3.0mol/L HCl aqueous solution, stirs and makes it abundant dissolving, measures 9mmol aniline then and adds in the above-mentioned solution, stirs 0.5h in 20 ℃ of ice-water baths, gets monomer mixed solution.Other takes by weighing the 20mmol ammonium persulphate and is dissolved in the 3.0mol/L HCl aqueous solution, stirs 0.5h to dissolving fully in 20 ℃ of ice-water baths, obtains colourless transparent solution.Speed with 1 of per second under static conditions drips ammonium persulfate aqueous solution in above-mentioned monomer mixed solution.After dropwising, continue to react to 24h.Reaction finishes, and gets 2mL reaction solution centrifuge washing, and sample is in order to do the test of polymkeric substance pattern, and the diameter of gained copolymer nano fiber is about 35～60nm, and length is 200～650nm.As shown in Figure 3.Residual reaction liquid is filtered, and filter cake drying under 60 ℃ got the deep green copolymer powder to constant weight in 7 days, and polymerization yield rate can reach 79%, and its specific conductivity is 0.67S/cm.
Embodiment 4
Take by weighing the adjacent methoxy of 5mmol-5-sulfoacid aniline, place the dried and clean beaker, add 0.5mol/L H
2SO
4The aqueous solution stirs and makes it abundant dissolving, measures 5mmol aniline then and adds in the above-mentioned solution, stirs 0.5h in 10 ℃ of ice-water baths, gets monomer mixed solution.Other takes by weighing the 5mmol Sodium Persulfate and is dissolved in 0.5mol/L H
2SO
4In the aqueous solution, in 10 ℃ of ice-water baths, stir 0.5h, obtain colourless transparent solution to dissolving fully.Speed with 1 of per second under static conditions drips sodium persulfate aqueous solution in above-mentioned monomer mixed solution.After dropwising, continue to react to 72h.Reaction finishes, and gets 2mL reaction solution centrifuge washing, and sample is in order to do the test of polymkeric substance pattern, and the diameter of gained copolymer nano fiber is about 45～65nm, and length is 200～750nm, as shown in Figure 4.Residual reaction liquid is filtered, and filter cake drying under 60 ℃ got the deep green copolymer powder to constant weight in 7 days, and polymerization yield rate can reach 59%, and its specific conductivity is 0.48S/cm.
Embodiment 5
Take by weighing the 1mmol diphenylamine sulfonic acid, place the dried and clean beaker, add the 2.0mol/L HCl aqueous solution, stir and make it abundant dissolving, measure 9mmol aniline then and add in the above-mentioned solution, in 25 ℃ of ice-water baths, stir 0.5h, get monomer mixed solution.Other takes by weighing the 15mmol Potassium Persulphate and is dissolved in the 2.0mol/L HCl aqueous solution, stirs 0.5h to dissolving fully in 25 ℃ of ice-water baths, obtains colourless transparent solution.Speed with 1 of per second under static conditions drips persulfate aqueous solution in above-mentioned monomer mixed solution.After dropwising, continue to react to 24h.Reaction finishes, and gets 2mL reaction solution centrifuge washing, and sample is in order to do the test of polymkeric substance pattern, and the mean diameter of gained copolymer nano fiber is about 78nm, and length is 200～600nm, as shown in Figure 4.Residual reaction liquid is filtered, and filter cake drying under 60 ℃ got the deep green copolymer powder to constant weight in 7 days, and polymerization yield rate can reach 80%, and its specific conductivity is 0.63S/cm.
Claims (10)
1. the static synthesis method of an aniline-sulfoacid aniline copolymer nano-fiber is characterized in that: under static conditions, be reaction medium solution with the acidic solution, aniline and sulfoacid aniline derivative are dissolved in reaction medium solution; Oxygenant is dissolved in a kind of reaction medium solution; Two kinds of solution are mixed, make oxygenant cause aniline and sulfoacid aniline derivatives monomer polymerization reaction take place, temperature of reaction is 0～30 ℃, and the reaction times is 1～72 hour, obtains containing the polymers soln of copolymer nano fiber; Polymers soln is filtered, and 60 ℃ were descended dry 7 days, and got aniline sulfoacid aniline copolymer nanofiber powder.
2. the static synthesis method of aniline sulfoacid aniline copolymer nanofiber according to claim 1 is characterized in that: the mol ratio of described aniline and sulfoacid aniline derivative 90: 10～50: 50; Described oxygenant is: a kind of in ammonium persulphate, Potassium Persulphate or the Sodium Persulfate; Described oxygenant and monomer total amount, promptly the mol ratio of the total amount of aniline and sulfoacid aniline derivative is 1: 4～2: 1; The molecular formula of described sulfoacid aniline derivative is as follows;
In the formula, R is respectively-H or-C
6H
4SO
3H; R
1Be respectively-H ,-SO
3H or-OCH
3R
2Be respectively-H or-SO
3H
3. the static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber according to claim 2, it is characterized in that: the mol ratio of the total amount of described oxygenant and aniline and sulfoacid aniline derivative is 1: 4～1: 1.
4. the static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber according to claim 1, it is characterized in that: when described aniline and sulfoacid aniline are dissolved in the reaction medium solution, total monomer, promptly the total mol concentration of aniline and sulfoacid aniline derivative is 0.025～0.5mol/L.
5. the static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber according to claim 4, it is characterized in that: when described aniline and sulfoacid aniline derivative are dissolved in the reaction medium solution, total monomer, promptly the total mol concentration of aniline and sulfoacid aniline derivative is 0.05～0.1mol/L.
6. the static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber according to claim 1 is characterized in that: described oxygenant is dissolved in in a kind of reaction medium solution the time, and the volumetric molar concentration of oxygenant is 0.025～0.5mol/L.
7. the static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber according to claim 6 is characterized in that: described oxygenant is dissolved in in a kind of reaction medium solution the time, and the volumetric molar concentration of oxygenant is 0.05～0.2mol/L.
8. the static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber according to claim 1, it is characterized in that: the reaction medium that uses is: a kind of as in concentration 0.2～3.0mol/L aqueous hydrochloric acid or the aqueous sulfuric acid of described acidic solution.
9. the static synthesis method of aniline-sulfoacid aniline copolymer nano-fiber according to claim 8, it is characterized in that: the concentration of described aqueous hydrochloric acid or aqueous sulfuric acid is 0.05～0.1mol/L.
10. according to the static synthesis method of claim 1,2,3,4,5,6,7,8 or 9 described aniline-sulfoacid aniline copolymer nano-fibers, it is characterized in that: preparation method's concrete steps are:
(1) preparation monomer solution: aniline and sulfoacid aniline derivative are joined in the reaction medium solution, stir and to make it abundant dissolving, form monomer solution, be put into then that constant temperature is to temperature of reaction in the reaction water-bath, described temperature of reaction is 0 to 30 ℃;
(2) preparation oxidizing agent solution: oxygenant is joined in the reaction medium solution identical with step (1), stir and to make it abundant dissolving, form oxidizing agent solution, be put into then and react that constant temperature is to temperature of reaction in the water-bath, temperature of reaction is 0 to 30 ℃;
(3) mixing solutions, polyreaction: the oxidizing agent solution of described step (2) is dropwise joined initiated polymerization in the monomer solution of described step (1);
(4) continue reaction: after oxygenant dropwises, continue reaction 1～72 hour under static state, temperature of reaction is 0～30 ℃, and it is reacted completely, and obtains containing the polymers soln of copolymer nano fiber;
(5) preparation copolymer nano fiber: polymers soln is filtered, 60 ℃ dry 7 days down, aniline sulfoacid aniline copolymer samples of nanopowders.
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